US 2525787 A
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Description (OCR text may contain errors)
Oct.. 17,. 195,0 fC', M, FQNTAN ET ,M 4 2,525,787
PROPYLENE POLYMERIZALT:0Ny PROCESS Filgd oct. s1. 41947 Patented Oct. 17, 1950 PnoPrLENE roLYMEmzA'rroN raooass Celeste M. Fontana, Pitman, N. J., Alex G. Oblad,
\ Dallas, Tex., and Glenn A. Kidder, Barbol,
Liberia, assignors., by mesne assignments, to
Socony-Vacuum Oil Company, Incorporated, New York, N. Y., a corporation of New` York Application October 31, 1947, Serial No. 783,320 14 claims. (cl. zso-ssalsi This invention relates to polymerization oi loleilns and relates more particularly to a process for the polymerization of propylene to produce polymer products having small changes in viscosity with changes in temperature.
It is well known that propylene can Vbe polymerlzed in the presence of suitable catalysts to produce polymer 4products having viscosities ranging from' those of light lubricating oils to those of heavy oils or even resins of plastic or semisolid nature. While these propylene polymer products have viscosities within the lubricating oil range or within the range of lubricating oil components, they have not attained wide acceptanceV aslubricating oils or lubricating oil components primarily because of their poor temperature-viscosity characteristics. Stated otherwise. these propylene polymers exhibit too great a change in viscosity with change in temperature, this characteristic being commonly expressed in terms of viscosity index (Dean and Davis, Chem. Met. Eng. 36, 318 (1929)), to make them acceptable for usel under conditions where they will be subjected to wide variations in temperature, as, for example, in internal combustion engines. at low temperatures they have high viscosities, tending to make starting diiilcult and to prevent rapid flow to moving parts while at higher temperatures, such as the normal propylene. It is another object of this invention toA provide a process for the production of highly l viscous polymersjfrom propylene. Itis another object of this invention to provide aprocess for the production of propylene polymers having high temperature-viscosity improving properties for blending with lubricating oil stocks. It is another object of this invention toproviclt propylene polymers having small changes in viscosity with changes in temperature. It is anothery object to afford prcpylene polymers suitable as lubricating oils or as blending agents in lubricating oils. particularly for use in internal combustion engines. It is another object to provide high viscosity propylene polymers. It is still another object of this invention to provide novel propylene polymers. Further objects of the invention will become apparent from thel following description thereof.
` In accordance with the invention. propylene polymers having small changes in viscosity with change in temperature are obtained in high yield by contacting propylene with aluminum lbromide dissolved in a nonpolymerizing hydrocarbon solvent in the presence of a catalyst promoting agent and correlating reaction conditions with respect to the ratio of the amount of catalyst promoting agent to the amount of dissolved aluminum bromide and the ratio of the amount of propylene monomer to the amount of dissolved aluminum bromide in the reaction mixture during the course of the reaction.
Correlationof reaction conditions is an essential element of the process producing the desired propylene polymer products. We have found that the essential reaction conditions producing the desired polymers are the ratio of promoter to dissolved aluminum bromide and the ratio of propylene` monomer to dissolved aluminum bromide. Since-the rate at which the propylene polymerizesis not readily ascertainable, itbecomes impractieable to attempt to set out the ratio of total olciln monomer in the reaction mixture todissolved aluminum bromide, and we therefore prefer to express this ratio as the rate atwhich the propylene monomer is added to the dissolved aluminum bromide. l
The desired propylene polymer products, having temperature-viscosity characteristics hereinafter defined, are obtained by employing a mol ratio of promoter, measured as hydrogen `bro-- mide, to dissolved aluminum fbromide of between about 02 to '5, and preferably between about 0.5 to 2.5, land a rate of addition of propylene to dissolved aluminum bromide not greater `than `2, and preferably not greater than i mol of 3 propylene per mol oi' dissolved aluminum bromide per minute. I
Commonly, temperature-viscosity characterisi c tics of lubricating oils have been expressed in terms of viscosity index. High viscosity index oils have small changes in viscosity with changes in temperature and low viscosity index oils have large changes in viscosity with changes in temperature. Viscosity index is calculated by comparison with arbitrarily selected natural reference oils and the viscosity index system of classification is quite satisfactory for those oils having viscosities comparable to the viscosities of the natural reference oils. However, for heavier lubricating oils having comparatively small changes in viscosity with changes in temperature, the viscosity system is unsatisfactory because it is not highly indicative of small differences in temperature-viscosity characteristics in the high viscosity range. Accordingly, recourse has been taken to the method of defining temperature-viscosity characteristics proposed by Walther (Erdol u. Teer 4, Nr. 29, 30 (1928), 5, Nr. 34 (1929), '7, 383 (1931)) which specifies the slope m of the curve on a chart having as coordinates: W=log` log (Csm-0.8) and log T, where Cst is viscosity in centistokes and T is the ai iolute temperature on the Fahrenheit scale. This constant m is essentially the slope of the viscosity curve on the A. S. T. M. Viscosity- Temperature Chart. The constant m will therefore be given by the expression where' W1 and Wa are calculated from the viscosity in centistokes at the temperatures Ti and T2 respectively, T2 being the higher temperature. For the purposes oi this invention, 'T2 will be regarded as 669.7 (210 F.) and T1 will be regarded as 559.7 (100 F.). It will be seen from this expression that those lubricating oils having better viscosity-temperature characteristics, i. e., those having smaller changes in viscosity with temperature, will have smaller values of m. In the present application, use will be made of these m values for characterizing the propylene polymers.
It will be realized that, for purposes of evaluating a lubricating oil in any particular type of lubrication operation or to compare two different oils with respect to fundamental properties, viscosity-temperature characteristics do not supply the complete answer since the absolute value of the viscosity at some given temperature must also be taken into consideration. For example, for some particular type of lubrication operation, an oil having a small change of viscosity with temperature may be required but unless the oil has, in addition to the required viscosity-temperature characteristics, a satisfactory viscosity at the maximum temperature of operation, or at the minimum temperature of operation as the case may be, it will not be satisfactory for the purpose. It thus becomes necessary in characterizing or comparing lubricating oils to define their properties not only by change of viscosity with temperature but also by viscosity at some particular temperature. Thus, oils have been characterized by giving their viscosities at 210 F. and their change in viscosity with temperature in terms of viscosity index, or as mentioned above, to avoid the drawbacks of the viscosity index system, in terms of their m values.
The propylene polymer products produced by the process of the present invention comprisel polymers having such viscosities and viscositytemperature characteristics that their m values will be numerically smaller than the m value given by the expression are exceptionally suited for admixture or blending with natural mineral oils or other types oi' oils since, in view of the superior viscosity-temperature characteristics of the polymers, the blends will have superior viscosity-temperature characteristics. These blends, and the polymers themselves where their viscosities are proper, are
particularly suited for use as automobile engine oils, aviation engine oils, etc.
The propylene polymers produced by the process of the present invention have viscosities at 210 F. ranging between 30 and 10,000 Saybolt Universal seconds. The equivalent values for W at 210 F. will be between 0.350 and +0.670, respectively, and, in accordance with the foregoing expression for m, will have m values smaller than 4.48 and 2.65, respectively. The products produced by the process of the invention include polymers having 210 F. viscosities in excess of 1,000 S. U. S. and in excess oi' 5,000 S. U. S., for example, between 5,000 S.,U. S. and 10,000 S. U. S.
In carrying out the process of the invention, We prefer to employ hydrogen bromide as the catalyst promoting agent. However, bromoalkanes containing at least three carbon atoms, such as propyl, isopropyl, butyl, isoamyl, etc.
bromo-alkanes, and compounds which react unbromide, to produce hydrogen bromide are also Y effective. The mechanism of the catalyst. promoting effect of the bromo-alkanes is not well understood although it appears that, since aluminum bromide is known to catalyze the dehydrobromination of bromo-alkanes, dehydrobromination oi the bromo-alkanes may occur to form oleiins and hydrogen bromide, the hydrogen bromide thereupon acting as the effective promoter. However, at low temperatures, equilibria do not favor dehydrobromination and at these temperatures it is possible that the promoting effect may be due to copolymerizaticn of the bromo-alkanes to produce a polymer and hydrogen bromide. It is also possible that the bromo-alkanes are in themselves promoting agents, and that where hydrogen bromide is present, a bromo-alkane is formed by reaction of the hydrogen bromide and the propylene which thereupon acts as the catalyst promoting agent.
'I'he concentration of dissolved aluminum bromide should be sumciently high to catalyze the polymerization reaction. An upper limit to catalyst concentration is placed primarily by the fact that in order to obtain maximum utilization of the catalyst a larger amount of propylene must be added to the reaction mixture with higher catalyst concentrations, and the addition of large amounts of propylene to the reaction mixture produces a highly viscous mixture which is anziane? r l difllcult to handle during thelater `operations of clarification, solvent recovery. etc. Preferably, we `employ a` catalyst concentration, based upon the total non-polymerizing hydrocarbon in the reaction mixture, of between 01 and 1.5 mol per cent. However, it will be understood that the maximum `concentration of aluminum bromide that may be employedwill be` limited by the solubility of the aluminum bromide in the particular solvent atthe temperature of polymerization employed.
The amount oi' be employed, as mentioned hereinabove, will be between 0.2 and 5.0` mos, preferably 0.5 to 2.5 mols of hydrogen bromide per mol of dissolved aluminum bromide. When employing bromoalkanes, etc.,'the mol ratio of these compounds to dissolved aluminum bromide may be the same numericallyA as the mol ratio of hydrogen bromide to dissolved aluminum bromide just mentioned. When employing, as catalyst promoting agents, compounds which react to form hydrogen4 bromide. such as water, etc., which react with the aluminum bromide to form hydrogen bromide, an amount should be used which will give uponreacti'onl the above mentioned ratios of hydrogen bromide to dissolved aluminum bromide.
It is possible to carry out the reaction either as a batch or a continuous operation. In batch operation, the propylene may be addedto the reaction vessel containing the dissolved alumin um bromide plus the proper amount of pro moter. In this type` of operation, the reaction vessel will contain a known amount of dissolved aluminum bromide, and the propylene may be added thereto at the desired rate within the limits above`mentioned. In continuous operation, the propylene and the dissolved aluminum bromide plus the proper amount of promoter in admixture with the propylene or as a separate stream .are added simultaneously to the reaction vessel, and a stream of reaction `mixture is reY moved continuously therefrom. In this latter type of operation, the reaction vessel will be nlled with reaction mixture and, for any given ratio of rates of flow of the respective streams entering therein, will contain a known quantity oi dissolved aluminum bromide. Thus, suitable adjustment of the rates of :dow of the respective streams will result in addition `of vprcpylene to the reaction vessel at the desired rate with respect to the aluminum bromide concentration.
The liquid catalyst may be prepared by dissolving the aluminum bromide in any suitable type of nonpolymerizing hydrocarbon solvent. Examples of suitable hydrocarbon solvents are the saturated hydrocarbon solvents such as ethane, propane, normal butane, etc. Mixtures ol' one or more solvents may also be employed, if desired, `for preparing the liquid catalyst.
It is preferred to carry out the polymerization reaction in the presence of a diluent for the propylene. The saturated hydrocarbons em.- ployed as solvents forthe aluminum bromide are satisfactory as diluents for the propylene, and mixtures of two or more of the saturated hydrocarbons may be used if desired. Ethylene may hydrogen bromide promoter to.
and another type of hydrocarbon maybe eniployed as solvent for preparing the liquid catalyst. However, it will usually be more convenient to employ the same `type of hydrocarbon as diluent and as solvent, .particularly in large* scale operations. in vorder to simplify the later procedures of recovering the solvent andrecovering. the diluent for reuse. In the case of Vlow temperature polymerization, on the otherhand, it may frequently be advantageous to use a solvent of moderate volatility, such as normal butane, to prepare the liquid catalyst, and a highly volatile diluent, such as ethane. capable of use for evaporative cooling to control the temperature of the polymerization reaction. The liquid catalyst may be added to part or all of the diluent, whether or not the same type of hydrocarbon is used as solvent for preparing the liquid catalyst and as diluent, and the mixture will serve in the capacity of both liquid catalyst and diluent. In this manner of operation, the mixture may be regarded as a liquid catalyst-diluent.
The process of the invention may be carried out at any desired temperature. between about -80 C. to +30 C. are satisfactory although higher and lower temperatures may be employed, if desired. As hereinabove mentioned, the viscosities of the propylene polymers obtained increase as the temperature of polymerization is decreased. Accordingly, in order to obtain a propylene polymer of desired viscosity, proper seas lubricating oilsare obtained.
alsobe usedas a diluent where the reaction con- .f The aluminum bromide may be dissolved by stirring thesolid compound with the saturated hydrocarbon solvent. However, solid aluminum brandde is diillcult to handle and to dissolve, and it 'is preferred to effect solution by melting the aluminum bromide by heating to a temperature of about 98 C. or higher and thereafter mixing while in the molten state with the saturated hydrocarbon solvent. 'I'he mixing is preferably carried outin a closed vessel or chamber whereby loss of saturated hydrocarbon as a result of heating by the molten aluminum bromide is avoided.
In carrying out the polymerization reaction,
the reactants before being charged'to the reactor are preferably brought to the desired reaction temperature The polymerization `reaction is exothermic, and, if desired, the temperature of the reaction mixture may be maintained at the desired reaction temperature by means of external heat exchangers, as, for example, by employing a jacketed reaction vessel, or by employing heat exchanger coils within `the reaction vessel through which suitable refrigerants may be passed. If desired, evaporative cooling maybe employed. At very low` temperatures of reaction, an internal refrigerant such as solid vcar-- bon dioxide may be added to the reaction mixture toprovide refrigeration or to supplement the cooling provided by other means.
Pressures to be employed should be suflicient to keep the solvent-diluent in the liquid phase Temperatures at the particular temperature of polymerization selected. The propylene may be admitted to the reactor in either the gas phase or the liquid I phase. Where it is desired to admit the propylene in the gas phase, the pressure within the reactor may be maintained sufliciently high to keep the solvent-diluent in the liquid phase but suiliciently low to keep the propylene in the gas phase at the temperature of admission.
Following polymerization, any catalyst tar in the reactor eilluent may be removed by settling. The dissolved aluminum bromide may then be removed from the reaction mixture and recovered for reuse, if desired. A suitable procedure for removing the dissolved aluminum bromide comprises extracting the reaction mixture with a hydrocarbon immiscible liquid in which the aluminum bromide is more soluble than in the reaction mixture. The hydrocarbon immiseible liquid may be formed by admixing at room temperature about 7p parts by weight of a 'metallic halide, preferably aluminum bromide, with 30 parts by weight of a hydrocarbon liquid, preferably highly branched, such as iso-octane or turpentine, for a period of time sufficient to form a homogeneous liquid. Another procedure vi'or removing the dissolved aluminum bromide comprises heating the reactor eiliuent to a high temperature, for example, about 80 C., for a` suillciently long period of time whereby the dissolved aluminum bromide forms with the solvent and diluent employed an insoluble tar which may be removed by settling. Where this procedure is employed, the removal of catalyst tar formed during the reaction may be postponed until after the dissolved aluminum bromide is converted into tar and removed along with this additional tar. It may be uneconomical to continue heating the reactor eiiluent for a sumcient period of time to completely remove the dissolved aluminum bromide as insoluble tar. In such cases, heating may be continued for a time suillcient to remove the greater proportion of the dissolved aluminum bromide after which the reaction mixture may be treated with water, alkali, alcohol, etc., to inactivate the catalyst. Thereafter, the reaction products of the dissolved aluminum bromide and the inactivating agent may be removed by washing,` filtering, or other suitable procedure. The portion of the dissolved aluminum bromide remaining after heat treatment may also be inactivated by treating the reaction products with activated clay such as bentonite provided such clay is not anhydrous. Such clays ordinarily` contain vsufficient water to inactivate the remaining portion of dissolved aluminum bromide and, when spent, may be regenerated With steam for further inactivation of catalyst. This latter` procedure of inactivating dissolved aluminum bromide has the advantage of concomitantly clarifying the reaction products. Such clarification of the reaction products may be desirable irrespective of the method employed for removing dissolved aluminum bromide, 4and the same types of clay as those mentioned above may be employed where clarification alone is the object to be achieved, although regeneration with steam will not be required. Following clarification, whether or not concomitant with removal of dissolved aluminum bromide, the reaction products may be subjected to fractionation, steam distillation, or other suitable procedure to remove solvent, diluent, and any light hydrocarbon reaction products from the desired polymer product.
The aluminum bromide removed by extraction miscible liquid or in the form of tar may be recovered therefrom for reuse by suitable procedures of heating followed by condensation of the volatilized aluminum bromide. Where the reaction products contain only small amounts of aluminum bromide, recovery of the aluminum bromide for reuse may not be economically desirable. In such cases, the reaction products may be treated with water, alkali, alcohol, etc., to react with the entire amount of aluminum bromide.
Hydrogen bromide promoter in the reaction eiliuent will be largely contained in the catalyst tar and will therefore be largely removed along with the tar. The remaining portion of the hy drogen bromide promoter will be removed from the reactor eiliuent during fractionation, steam distillation, or otherwise for the removaLof solvent, diluent, and any light hydrocarbon products. Where bromo-alkanes are employed as promoters, they likewise will be largely contained in the catalyst tar and will be largely removed from the reactor eiiluent along with catalyst tar, and the remainder will be removed during the procedures for the removal of solvent or diluent in similar manner to the hydrogen bromide. Where compounds reacting to form hydrogen bromide are employed as promoters, any solid residue such as aluminum hydroxide will be removed by filtration, and any liquid reaction products will'be removed along with the solvent or diluent. Should any hydrogen bromide remain in the polymerproduct after removal of the solvent and diluent, it will be removed at the temperatures subsequently employed in fractionation for separation of light polymer products from the desired heavier polymer products. For fractionation from the desired polymer product of any light polymer products that may be formed, low pressures are maintained within the fractionation apparatus to obtain ei'- fective separation without the use of high temperatures conducive to cracking of the polymer product. Temperatures not above about 300 C. are satisfactory, and the pressure within the apparatus may be progressively decreased, as the fractionation proceeds, to a pressure of about 1 millimeter of mercury'at the end of the fractionation operation.
The accompanying drawing is a flow sheet illustrating one embodiment of my invention.
Referring now to the drawing, propylene feed enters the system through line 5 and is pumped Yby means of pump 6 to polymerization reactor l.
Before entering the polymerization reactor, the propylene feed passes through heat 'exchanger 9 in line 5, where it is heated or cooled to the desired reaction temperature. 'I'he solvent-diluent feed enters the system through line l0 and is pumped by means of pumps Il and I2 to the polymerization reactor 1, being heated or cooled to the desired reaction temperature before entering the reaction by passage through heat exchanger i4 in line I0.
y Solid aluminum bromide is melted in melter I5 provided with cover i6, stirrer il, and heating Jacket I9 through which steam or other suitable f heating medium may be passed. The molten with valve 24. To assist in solution of the aluminum bromide, the solvent-diluent and molten aluminum bromide in drum 2| is stirred by means of stirrer 25. The dissolved aluminum bromide is then passed from the mixing drum through line 2B to the main portion of the solvent-diluent feed in line l0.
Hydrogen bromide promoter is fed to the system through line 21 connected to line Ill entering the polymerization reactor 1. Recycle solventdiluent obtained in the manner to be hereinafter explained enters line Il) through line 29 and passes into polymerization reactor 1. Line 29 is provided with flow control valve 3D and diluent feed line lll is provided with flow control valve 3| for control of the total amount of solvent-diluent entering the reactor 1. Propylene feed line 5 is provided with flow control valve 32, hydrogen bromide feed line 21 is fitted with now control valve 34, and molten aluminum bromide line is fitted with flow control valve 35. By suitable manipulation of these ow control valves, the proper ratio of hydrogen bromide to aluminum bromide, the desired concentration of aluminum bromide, and the proper rate of proplylene feed to aluminum bromide concentration is obtained in the polymerization reactor 1.
The solvent-diluent feed containing the dissolved aluminum bromide and hydrogen bromide is `intimately mixed with the propylene in the reactor 1 by means of stirrer 35. To maintain the reactants at the desired polymerization temperature, a suitable heating or cooling medium is conducted through jacket 31. The polymerization reaction products are withdrawn from the reactor 1 through line 39 and pumped by means of pump 39 to heating vessel 40 wherein the reaction products are heated to precipitate the dissolved aluminum bromide by formation of insoluble tar with the solvent-diluent. Heating Vessel 4|) is provided with a jacket 4| through which a suitable heating medium such as steam may be circulated and with a st'rrer 42 to obtain efiicient heat transfer between the walls of the vessel and the polymerization reaction products. The mixture of reacton products and insoluble tar is passed through line 43 to separator 44 wherein the tar formed during the polymerization reaction and in heating vessel settles to the bottom of the separator. The tar is withdrawn from the separator through line 45 and may then be sent, if desired. to a recovery system (not shown) for recovery of the aluminum bromide. i
The polymerization reaction products now free of the greater proportion of dissolved aluminum bromide leave the separator through line 4B and are pumped by means of `pump 41 through clay solvent-diluent and the greater part of any remaining hydrogen bromide promotor are removed as overhead through line 56. The overhead passes through condenser 51 -wherein the solvent-diluent is condensed and cooled to the desired reaction temperature in reactor 1, and the condensate is pumped by pump 58 to receiver 59. i From receiver 59, the solvent-diluent is pumped by means of pump 60 through line 29 to line Il) for recycle to the polymerization reactor 1.. The recycle solvent-diluent may contain some hydrogen bromide which enters the polymerization reactor in addition to the hydrogen bromide fed into the reactor from line 21. Accordingly,
this amount of hydrogen bromide must be taken into account when controlling the amount yof hydrogen bromide fed from line 21 to obtain the desired ratio of hydrogen bromide to aluminum bromide.
The bottoms from fractionating column 55 comprise the desired polymer product and any light polymer products formed during the reaction. In addition, the bottoms contain any hydrogen bromide promotor not removed during the fractionation operation. The bottoms are transferred through line 52 to fractionation column El where the light polymer products are removed as overhead through l'ne 64 and condensed in condenser to be utilized as desired. Fractionation column 6I is operatd at a much higher temperature than fractionation column 55 and at a low pressure, and any hydrogen bromide promoter not removed in column 55 will be removed in column 6I as overhead with the light polymer products. The desired polymer product is removed as bottoms from column 5l through line 66.
The above-described procedure is susceptible of various modifications. of employing the clay chambers 48 and 49, the polymerization reaction products in line 46 may be clarified by admixing with clay and thereafter filtering the clay therefrom. Additionally, if desired, the polymerization products issuing as bottoms from the fractionating column 55 may be steam distilled or otherwise treated for removal of any light polymer products. These andi other modifications are possible, and they, as well as the necessary provision of apparatus andalines,`
may be readily made by those skilled in the art The following examples are illustratye of thc types of products obtainable by the process of the In each example, propylene was prevent contact of the reactor' contents with order that continuous operation may be obtained by leaving one chamber on stream while the other chamber is taken off stream for refilling or for regeneration of the clay. Regeneration of the clay for removal of the remaining portion of bers pass through line 53` and are pumped by 4 pump 54 to fractionating column 55 where the moist air to avoid reaction with the -aluminum bromide thereby forming hydrogen bromide; Reactor eilluent was discharged into a Dewar vessel and admixed with isopropyl alcohol to quench and precipitate the dissolved aluminum bromide.
The clear supernatant liquid was decanted and the remainder `of the product mixture lclarified with bentonite clay. The product mixture was then stripped toa temperature of C. at 1 mm. pressure. The reaction conditions and the `results are set forth in Table `I.` Yields in each example were approximately 98 by weight based upon the amount of propylene charged.
For example, in place i asoma? Table I Ratio oi Viscosityat 210 F. Viscosity at 100 F. T Conc. oi Promoter to inofhgs 'm as m from Example sa? AlBra. AlBra. Mola Prop 'lene/ Wqat calcw formula Numb o. g/m1 dfifggtg, M01 111m/ s. U. s. ou. s. U. s. on. 21 F- ima "a-48,
1 19. 0 0. 0021 1.01 0. 513 50. 6 7. 47 298 6L 5 0. 043 3. 81 3. 9e 1. 7 0.00231 1. 02 0. 280 51. 7 7. 8 327 70. 8 -0. 034 3.87 3. 91 26 0.0100 1.00 0. 190 121 24.5 1, 501 325 0. 146 3. E 3. 59 0. 0 0. 0100 1. 51 0.201 inl 27. 5 2. 498 541 0. 161 3. 64 3. 56 2. 9 0. 0m 0. 55 0.103 129 22, 880 4, 950 0.325 3.11 3. 27 1. 0 0. 010 1. 50 0. 194 M 214 32, 640 7, 065 0. 368 2. 79 3. 19 2. 0 0. 010 1. 02 0.198 1, 3 91 29S 81, 900 17, 72) 0.394 3. 01 3. 14 -1 0 0. 0162 1. 40 0. 112 1.3.95 299 37, 700 8, 167 0. 394 2. 55 3.14 2 2 0. 010 1. 00 0. m4 1, 542 331 58, 700 12, 695 0.402 2. 72 3.13 5. 5 0. 00163 0. 928 0. m3 1, 709 305 106, 500 23, 070 0. 409 2. 90 3. 12 1. 0 0. 010 1. a) 0.197 1, 766 378 67, 200 14, 540 0. 411 2. 67 3. 11 2. 0 0.010 1. 50 0. 197 2, 178 468 110, 380 23, 892 0.427 2. 70 3. 08 -6. 0 0. 00326 0. 917 0. 206 2, 240 482 164, 600 35,620 0. 429 2. 94 3.08 40 0. 0125 l. 23 0. 984 4, 450 954 440, 500 95, 350 0. 474 2.85 3. 00 2P 0. 010 1. 55 0.198 5, 191 1, 112 465, 000 98, 480 0. 483 2. 77 2. 98 30 0. (D163 0. 290 0. 190 6, 242 1, 333 669, 000 144, 700 O. 497 2. 78 2. 90
In Example G, the promoter was isoamyl bromide. In Example 12, the promoter was isoproplyl bromide. In all other examples. the promoter was ydrogen bromide.
In order to more clearly indicate the improved results to be obtained by the process of the invention, the following examples are given wherein the reaction conditions employed were outside the limits hereinabove set forth. The examples were carried out in substantally the same manner as described above in connection with the examples in Table I. The reaction conditions and the results are set forth in Table II.
polymerizing hydrocarbon solvent, and a catalyst promoter selected from the group consisting of hydrogen bromide, bromo-alkanes containing at least three carbon atoms, and compounds which react under the conditions of the reaction to produce hydrogen bromide, in a polymerization reaction zone, in proportions such that during the course of the reaction, the mol ratio of catalyst promoter to dissolved aluminum bromide in the Table II Ratio ol Rate o, Ad Viscosity at 210 F. Viscosity at 100 F. i mp1. 15,13% 229.22 1113323.12 egg1ggg; Us .21.52% unibet s Mo S/Mo romoter m- C. solvent AdilegQdol olllBrx/ S. U. S. Ct. S. U. S Ost. lated Lmw 31. 0. 000895 0 2. 04 135. 5 28. 09 3, m3 693. 2 0.164 3. 71 3. 56 23 0. 0050 1. 30 8. 84 375 80. 2 18, 870 4, 085 0. 281 3. 55 3. 35 11. 7 0. 00041 0 1. 31 448 96. 2 26, 038 5, G36 0. 298 3. 55 3. 32 0. 00163 0. 0l 5.09 930 199 87, 000 18,830 0.362 3. 45 3. '1X1 -30 0. 00228 0 0. 95 1, 094 234 110, 600 25, 240 0. 375 3. 45 3.18 -30 0. 00217 0 3. 05 l, 152 247 141, 000 30, 500 0. 379 3. 50 3.17
In each example, the promoter was hydrogen bromide.
It will be seen from Table I that the m values of the polymer products of the invention are lower than the m values obtained from the expression Also, it will be seen from Table II that the m values of the polymer products produced by processes other than that disclosed in the present application are higher than those obtained from the expression.
Having thus described our invention, it is to be understood that such description has been given by way of illustration and example only and not by way of limitation, reference for the latter purpose being had to the appended claims.
1. A process Vfor the production ot a propylene polymer having a change in viscosity with temperature smaller than that given by the expression and W=1og1og (Csm-r0.8), 'n being 559.'z and T: being 669.7, which comprises admixing propylene, aluminum bromide dissolved in a nonpolymerization reaction zone will be between 0.2 and 5.0 and the rate o! addition of propylene to dissolved aluminum bromide in the polymerization reaction zone will be not greater than 2 l'nols of propylene per mol of dissolved aluminum bromide per minute.
2. The process of claim 1 wherein tie nonpolymerizing hydrocarbon solvent is a low boiling saturated hydrocarbon solvent.
3. The process oi' claim 1 wherein the nonpolymerizing hydrocarbon solvent is normal butane.
4. The process of claim 1 wherein the nonpolymerizing hydrocarbon solvent is propane.
5. The process of claim 1 wherein the catalyst promoter is hydrogen bromide.
6. A process for the production of a propylene polymer having a change in viscosity with temperature smaller than that given by the expression and W=1og log (Cstrz+0.8), T1 being 559.7 and Tz being 669.7, which comprises admixing propylene with aluminum bromide dissolved in a nonpolymerizing hydrocarbon solvent at a rate not greater tuanzmols otpiowleneper mol ci aluminum bromide per minute and maintaining in said reaction mixture hydrogen bromide ,in a concentration ybetween about 0.2 and 5.0 mols per mol oi aluminum bromide. l c
'1. A process .for the production of a propylene -polymer having a change in viscosity with 4temperature smaller than that given by the expression w trasse-lauw where A l g 10g (outgrow-10g log (cam-ros) 10g Tg-iog T1 Tr being 669.72 which comprises propylene, aluminum bromide dissolved in a nonpolymerizing hydrocarbon solvent. and a catalyst promoter selected from the group consisting of hydrogen bromide. bromo-alkanes containing at least three carbon atoms, and compounds and W=log log (Cstr, +0.8), T1 being 559.7 and T: being 669.'I, which comprises adding propylene to aluminum bromide dissolved in a nonpolymerizing hydrocarbon solvent at a rate not greater than 2 mols of propylene per mol o! dissolved aluminum bromide per minute. said dissolved aluminum bromide containing between 0.2 and 5.0 mols for each mol of dissolved aluminum bromide of a catalyst promoter selected from the group consisting oi hydrogen bromide, bromoalkanes containing at least three carbon atoms. and compounds which react under the conditions of the reaction to produce hydrogen bromide.
9. A process for the production of a propylene polymer having a change in viscosity with temperature smaller than that given by the expression where f log log (Cstr1+0.8)log log (Cst,-,+0.8) m log Tg-log T1 and W=iog log (Cstzg-l-O), T1 being 559.7 and and W=1og1og cstn+o.s), 'r1 being 55er andadmiring *asomar 14 e'rthan 2 mols of propylene `bei minute pervinol o! dissolved aluminum" bromide contained in said 4polymerization reaction zonepremoving eilluent from `said polymerization reactionrzone. removing nonpolymerizing hydrocarbon solvent from" said "eiiluent, recycling said solventio dissolveiurther amounts of said aluminum bromide catalyst.` removinglight polymer products from said emuent, and recovering from said eilluent propylene polymerproductf.` i
` 10. A continuous process for the production o! apropylene polymer having a change in viscosity with temperature smaller than `that given by the i expression m=3.s5o-1.794W where i log log (CstT,+0.8)-log log (CstTz-,I-O) m: log Tg-log T, i
and W=1eg1og (comme), 'r1 being 55a7 and Tr being 669.7", which comprises passing to a polymerization reaction zone a stream oi alumibetween 0.2 and 5.0 mols of catalyst promoter per mol of` dissolved aluminum bromide and a stream of propylene at a rate not greater than 2 mols of propylene per mol o! dissolved aluminum bromide per minute.
11. As a composition of matter, a propylene polymer having a change in viscosity with temperature smaller than that given by the expression m=3.850-1.794W where y log 10g (CstTt-l-O) -log log (Cstyz+0.8) mlog Tg-log T1 duce hydrogen bromide, in a polymerization reaction zone,fin proportions such that during the course ci the reaction, the mol ratio of catalyst promoter to dissolved aluminum bromide in the polymerization reaction zone will be between 0.2 and 5.0 and the rate of addition of propylene to dissolved aluminum bromide in the polymerization reaction zone will be not greater than 2 mols o! propylene per mol of dissolved aluminum bromide per minute.
12. As a composition of matter, a propylene polymer having a viscosity at '210 F. between 30 Saybolt Universall seconds and 10,000 Saybolt Universal seconds and having a change in viscosity with temperature smaller than that given by the expression least three carbon atoms, and compounds which react under the conditions-of the reaction to produce hydrogen bromide, in a polymerization reaction zone, in proportions such that during the courseA ofthe reaction, the mol ratio of catalyst promoter to dissolved aluminum bromide in the polymerization reaction zone will be between 0.2 and 5.0 and the rate of addition of propylene to dissolved aluminum bromide in the polymerization reaction zone will be not greater than 2 mols of propylene per mol of dissolved aluminum bromide per minute.
13. As a composition of matter, a propylene polymer having a 210 F. viscosity in excess of 1,000 Saybolt Universal seconds/and having a change in viscosity with temperature smaller than that given by the expression 14. As a composition of matter, a propylene polymer havinga 210 F..viscosity in excess of 5,000 Saybolt Universal seconds' and having a change in viscosity withv temperature smaller than that given by the expression =3.8501.794W where i log logl(CstTl+0.8) log log (CstTI-i-O) m= 10g Tg-log T1 and W=1og log (CstTa-i-O), T1 being 559.7 and T2 being 669.7, said propylene polymer being obtained by the process which comprises admixlng propylene, aluminum bromide dissolved in a nonpolymerizing hydrocarbon solvent, and a catalyst promoter selected from the group consisting of hydrogen bromide, bromo-alkanes containing at least three carbon atoms, and compounds which react under the conditions of the reaction to produce hydrogen bromide, in a polymerization reaction zone, in proportions such that during the course of the reaction, the mol ratio of catalyst promoter to dissolved aluminum bromide in the polymerization reaction -zone will be between 0.2 and 5.0 and the rate of addition -oi! propylene to dissolved aluminum bromide in the polymerizaand W=1og1og (cam-0.8), Tl being 559m and 3 T2 being 669.7 said propylene polymer being obtained by the process which comprises admlxing propylene, aluminum bromide dissolved in a nonpolymerizing hydrocarbon solvent, and a catalyst promoter selected from the group consisting of hydrogen bromide, bromo-alkanes containing at least three carbon atoms. and compounds which react under the conditions of the reaction to produce hydrogen bromide, in a polymerization reaction zone, in proportions such that during the course of the reaction, the mol ratio of catalyst promoter to dissolved aluminum bromide in the polymerization reaction zone willbe between 0.2 and 5.0 and the rate of addition of propylene to dissolved aluminum bromide in the polymerization reaction zone will be not greater than 2 mols of propylene per mol of dissolved aluminum bromide per minute.
tion reaction zone will be not greater than 2 mols of propylene per mol of dissolved aluminum bromide per minute.
CELESTE M. FONTANA.
ALEX G. OBLAD.
GLENN A. KIDDER.
REFERENCES CITED The following references are of record in the ille of this patent:
UNITED STATES PATENTS Number Name Date 2,317,878 Bannon Apr. 27, 1943 2,397,945 Burney et al Apr. 9, 1946 2,401,933 Hersberger June 11, 1946 OTHER REFERENCES Thomas, Anhydrous Aluminum Chloride in Organic Chemistry, Reinhold Publ. Corp. (1941), page 875.